WO2018066239A1 - Glass material and method for manufacturing same - Google Patents

Glass material and method for manufacturing same Download PDF

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Publication number
WO2018066239A1
WO2018066239A1 PCT/JP2017/029676 JP2017029676W WO2018066239A1 WO 2018066239 A1 WO2018066239 A1 WO 2018066239A1 JP 2017029676 W JP2017029676 W JP 2017029676W WO 2018066239 A1 WO2018066239 A1 WO 2018066239A1
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Prior art keywords
glass
glass material
present
content
light transmittance
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PCT/JP2017/029676
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French (fr)
Japanese (ja)
Inventor
太志 鈴木
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日本電気硝子株式会社
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Priority claimed from JP2017080501A external-priority patent/JP2018062457A/en
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to CN201780057494.9A priority Critical patent/CN109715575B/en
Priority to US16/331,563 priority patent/US10829406B2/en
Publication of WO2018066239A1 publication Critical patent/WO2018066239A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0085—Compositions for glass with special properties for UV-transmitting glass
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/09—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on magneto-optical elements, e.g. exhibiting Faraday effect
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2203/00—Production processes
    • C03C2203/10—Melting processes

Definitions

  • the present invention relates to a glass material suitable for a material of a magneto-optical element constituting a magnetic device such as an optical isolator, an optical circulator, a magnetic sensor, a magnetic glass lens used for a digital camera, a glass sheet used for a band-pass filter, and the like. It relates to the manufacturing method.
  • a glass material containing terbium oxide which is a paramagnetic compound, exhibits a Faraday effect which is one of magneto-optical effects.
  • the Faraday effect is an effect of rotating the polarization plane of linearly polarized light passing through a material placed in a magnetic field. Such effects are used in optical isolators, magnetic field sensors, and the like.
  • the optical rotation (rotation angle of the polarization plane) ⁇ by the Faraday effect is expressed by the following equation, where H is the strength of the magnetic field and L is the length of the substance through which the polarized light passes.
  • V is a constant depending on the type of substance, and is called Verde's constant.
  • the Verde constant is a positive value for a diamagnetic material and a negative value for a paramagnetic material. The greater the absolute value of the Verde constant, the greater the absolute value of the optical rotation, resulting in a large Faraday effect.
  • the above glass material shows high transmittance in the visible range to infrared range (for example, 420 to 1500 nm), but shows light absorption by the terbium element itself in the short wavelength range (for example, 420 nm or less). Therefore, there is a problem that the light transmittance is reduced in a short wavelength region and the light extraction efficiency of the magneto-optical device is inferior.
  • an object of the present invention is to provide a glass material capable of achieving both a high Faraday effect and a high light transmittance in a short wavelength region.
  • the glass material of the present invention is characterized by containing Pr 2 O 3 30 to 50% and B 2 O 3 + P 2 O 5 0.1 to 70% in mol%.
  • B 2 O 3 + P 2 O 5 means the total content of B 2 O 3 and P 2 O 5 .
  • Pr 2 O 3 basically exhibits no light absorption in a wavelength region of 420 nm or less (for example, 250 to 420 nm), and thus exhibits high transmittance in the wavelength region.
  • the ultraviolet absorption edge of the glass is in the vicinity of 400 nm, the glass itself absorbs ultraviolet light even if there is no Pr 2 O 3 absorption, leading to a decrease in transmittance at 420 nm or less. Since it has been found that the ultraviolet absorption edge of the glass shifts to the short wavelength side by including at least one of B 2 O 3 and P 2 O 5 as an essential component, the present invention has been proposed. Furthermore, since B 2 O 3 and P 2 O 5 are glass skeleton components, they have a feature that they are easily vitrified even if they contain a large amount of Pr 2 O 3 . Thereby, even if the diameter of the glass material is increased, it becomes difficult to crystallize, so that productivity can be improved.
  • the glass material of the present invention preferably further contains Al 2 O 3 0 to 50% in mol%. In this way, vitrification becomes easier.
  • the glass material of the present invention preferably has a thickness of 1 mm and a shortest wavelength at which the light transmittance is 60% is 350 nm or less. In this way, it is possible to improve the light extraction efficiency of the magneto-optical device in the short wavelength region.
  • the glass material of the present invention can be used as a magneto-optical element.
  • the glass material of the present invention can be used as a Faraday rotation element which is a kind of magneto-optical element. By using it for the above application, the effects of the present invention can be enjoyed.
  • the method for producing a glass material of the present invention is a method for producing the above glass material, and in a state where the glass raw material lump is suspended and held in the air, the glass raw material lump is heated and melted to obtain a molten glass. And a step of cooling the molten glass.
  • a glass material is produced by melting a raw material in a melting container such as a crucible and cooling (melting method).
  • a melting container such as a crucible and cooling (melting method).
  • the glass material of the present invention has a composition containing a large amount of Pr 2 O 3 that basically does not constitute a glass skeleton as described above, and is a material that is difficult to vitrify. Therefore, in a normal melting method, There is a possibility that crystallization proceeds from the contact interface with the melting vessel.
  • composition Even if the composition is difficult to vitrify, it can be vitrified by eliminating contact at the interface with the melting vessel.
  • a containerless floating method in which a raw material is melted and cooled in a suspended state is known. When this method is used, since the molten glass hardly comes into contact with the melting vessel, crystallization starting from the interface with the melting vessel can be prevented, and vitrification becomes possible.
  • the glass material of the present invention can achieve both a high Faraday effect and a high light transmittance in a short wavelength region, and is particularly suitable as a Faraday rotating element of a magneto-optical device in a short wavelength region.
  • the glass material of the present invention contains Pr 2 O 3 30 to 50% and B 2 O 3 + P 2 O 5 0.1 to 70% in mol%. The reason for limiting the glass composition range in this way will be described below. In the following description of the content of each component, “%” means “mol%” unless otherwise specified.
  • Pr 2 O 3 is a component that increases the Faraday effect by increasing the absolute value of the Verde constant.
  • the content of Pr 2 O 3 is 30 to 50%, preferably 30 to 49%, 31 to 48%, particularly preferably 32 to 47%.
  • the absolute value of the Verdet constant is reduced, a sufficient Faraday effect is difficult to obtain.
  • the content of Pr 2 O 3 is too large, the ultraviolet absorption edge of the glass tends to shift to the long wavelength side. Also, vitrification tends to be difficult.
  • the content of Pr 2 O 3 in the present invention is a representation in terms of Pr present in the glass to the oxide of any trivalent.
  • the magnetic moment that is the origin of the Verde constant is larger in Pr 3+ than in Pr 4+ . Therefore, the larger the ratio of Pr 3+ in the glass material, the greater the Faraday effect, which is preferable.
  • the ratio of Pr 3+ in the total Pr is preferably 50% or more, 60% or more, 70% or more, 80% or more, particularly 90% or more in mol%.
  • B 2 O 3 and P 2 O 5 are components for forming a glass skeleton and expanding the vitrification range. Further, by containing these components, the ultraviolet absorption edge can be shifted to the short wavelength side. However, since these components do not contribute to the improvement of the Verde constant, if the content is too large, it is difficult to obtain a sufficient Faraday effect. Therefore, the total content of B 2 O 3 and P 2 O 5 is 0.1 to 70%, 0.5 to 69%, 1 to 68%, 2 to 67%, 3 to 66%, It is particularly preferably 4 to 65%.
  • a preferable content of each component of B 2 O 3 and P 2 O 5 is as follows.
  • the content of B 2 O 3 is 0 to 70% (excluding 70%), 0.1 to 69%, 1 to 68%, 2 to 67%, 3 to 66%, particularly 4 to 65%. It is preferable.
  • the content of P 2 O 5 is preferably 0 to 70%, 0.1 to 60%, 1 to 55%, 2 to 50%, 3 to 48%, 4 to 47%, particularly preferably 5 to 46%. .
  • the glass material of the present invention can contain various components shown below.
  • Al 2 O 3 is a component that forms a glass skeleton as an intermediate oxide and widens the vitrification range.
  • the content of Al 2 O 3 is preferably 0 to 50%, 0.1 to 40%, 1 to 30%, 1 to 20%, particularly 1 to 10%.
  • SiO 2 is a component that contributes to glass formation and widens the vitrification range. However, when the amount of SiO 2 increases, the ultraviolet absorption edge of the glass tends to shift to the long wavelength side. Therefore, the content of SiO 2 is preferably 0 to 40%, 0 to 35%, 0 to 30%, 0.1 to 25%, particularly 1 to 20%.
  • La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and Y 2 O 3 have the effect of improving the stability of vitrification. However, if the content is too large, it becomes difficult to vitrify. Further, it causes a decrease in light transmittance. Therefore, the contents of La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 and Y 2 O 3 are each preferably 10% or less, particularly preferably 5% or less.
  • Tb 2 O 3 , Dy 2 O 3 , Eu 2 O 3 , and Ce 2 O 3 contribute to the improvement of the Verde constant, but cause a decrease in light transmittance. Therefore, the contents of Tb 2 O 3 , Dy 2 O 3 , Eu 2 O 3 , and Ce 2 O 3 are each preferably 10% or less, 5% or less, and particularly preferably 1% or less.
  • the contents of Tb 2 O 3 , Dy 2 O 3 , Eu 2 O 3 , and Ce 2 O 3 are expressed by converting Tb, Dy, Eu, and Ce present in the glass into trivalent oxides. It is a thing.
  • the content of these components is preferably 0 to 10%, particularly 0 to 5%.
  • Ga 2 O 3 has the effect of increasing the glass forming ability and expanding the vitrification range. However, when there is too much the content, it will become easy to devitrify. Further, since the Ga 2 O 3 it does not contribute to the improvement of the Verdet constant, when the content is too large, a sufficient Faraday effect difficult to obtain. Therefore, the Ga 2 O 3 content is preferably 0 to 6%, particularly preferably 0 to 5%.
  • Fluorine has the effect of increasing the glass forming ability and expanding the vitrification range. However, if its content is too large, it may volatilize during melting and cause composition fluctuations, or it may adversely affect the stability of vitrification. Accordingly, the fluorine content (F 2 conversion) is preferably 0 to 10%, 0 to 7%, particularly preferably 0 to 5%.
  • Sb 2 O 3 can be added as a reducing agent.
  • the content of Sb 2 O 3 is preferably 0.1% or less in order to avoid coloring or in consideration of environmental load.
  • the ultraviolet absorption edge has a short wavelength. Therefore, it is preferable that the shortest wavelength at which the light transmittance is 60% at a thickness of 1 mm is 350 nm or less, 345 nm or less, 340 nm or less, 330 nm or less, 320 nm or less, particularly 300 nm or less.
  • This light transmittance is an external transmittance including reflection.
  • FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing apparatus for producing a glass material by a containerless floating method.
  • FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing apparatus for producing a glass material by a containerless floating method.
  • the manufacturing method of the glass material of this invention is demonstrated, referring FIG.
  • the glass material manufacturing apparatus 1 has a mold 10.
  • the mold 10 also serves as a melting container.
  • the molding die 10 has a molding surface 10a and a plurality of gas ejection holes 10b opened in the molding surface 10a.
  • the gas ejection hole 10b is connected to a gas supply mechanism 11 such as a gas cylinder. Gas is supplied from the gas supply mechanism 11 to the molding surface 10a via the gas ejection hole 10b.
  • the type of gas is not particularly limited, and may be, for example, air or oxygen, or a reducing gas containing nitrogen gas, argon gas, helium gas, carbon monoxide gas, carbon dioxide gas, or hydrogen. Good.
  • the glass raw material lump 12 is first arrange
  • the glass raw material block 12 for example, a raw material powder integrated by press molding or the like, a sintered body obtained by integrating raw material powder by press molding or the like, and a composition equivalent to the target glass composition are used. For example, an aggregate of crystals.
  • the glass raw material block 12 is floated on the molding surface 10a by ejecting gas from the gas ejection holes 10b. That is, the glass raw material block 12 is held in a state where it is not in contact with the molding surface 10a. In this state, the glass material block 12 is irradiated with laser light from the laser light irradiation device 13. Thereby, the glass raw material lump 12 is heated and melted to be vitrified to obtain molten glass. Thereafter, the glass material can be obtained by cooling the molten glass.
  • the glass material of the present invention since the glass material of the present invention has a high magnetic susceptibility, the glass material of the present invention is used for autofocus lenses such as digital cameras and camera-equipped mobile phones by molding into a lens shape by mold press molding or the like. Can do.
  • These cameras are provided with a driving device for changing the focal length of the camera, that is, for moving the autofocus lens to a predetermined position.
  • the driving device Conventionally, the driving device has a lens for fixing the lens.
  • a spring for moving the holder and the lens holder is provided.
  • a driving device including a lens holder and a spring a digital camera, a camera-equipped mobile phone type, or the like cannot be downsized.
  • a lens is made of the glass material of the present invention having a high magnetic susceptibility, the lens itself can be moved by a magnet, so that a lens holder and a spring are not required, and the camera and the like can be miniaturized.
  • the glass material of the present invention has a light transmittance in the wavelength region of 250 to 420 nm higher than that in the wavelength region of 420 to 500 nm, and a light transmittance of 550 to 620 nm in the wavelength region of 500 to 550 nm.
  • the light transmittance in the wavelength range of 620 to 950 nm is higher than the light transmittance in the wavelength range of 950 to 1200 nm.
  • it since it has the property of absorbing light in a specific wavelength region, it can be used as a band-pass filter by forming the glass material of the present invention into a sheet shape by polishing or the like.
  • Table 1 shows examples and comparative examples of the present invention.
  • Each sample was prepared as follows. First, raw materials prepared so as to have the glass composition shown in the table were press-molded, and sintered at 800 to 1400 ° C. for 6 hours to prepare glass raw material blocks.
  • the glass raw material lump was coarsely pulverized in a mortar to obtain small pieces of 0.05 to 1.5 g.
  • a glass material (diameter: about 1 to 10 mm) was produced by a containerless floating method using an apparatus according to FIG. A 100 W CO 2 laser oscillator was used as the heat source. Further, nitrogen gas was used as a gas for suspending the raw material lump in the air and was supplied at a flow rate of 1 to 30 L / min.
  • the Verde constant of the obtained glass material was measured using a Kerr effect measuring device (manufactured by JASCO Corporation, product number: K-250). Specifically, the obtained glass material was polished to a thickness of about 1 mm, the Faraday rotation angle at a wavelength of 400 to 850 nm was measured in a magnetic field of 15 kOe, and the Verde constant at a wavelength of 400 nm was calculated. The wavelength sweep rate was 6 nm / min. The results are shown in Table 1.
  • the shortest wavelength at which the light transmittance was 60% was measured using a spectrophotometer (Shimadzu UV-3100) after polishing the obtained glass material to a thickness of 1 mm.
  • the light transmittance is an external transmittance including reflection.
  • the glass materials of Examples 1 to 5 had a Verde constant of ⁇ 0.74 to ⁇ 1.87 at a wavelength of 400 nm, and had a large absolute value. Further, the shortest wavelength at which the light transmittance reached 60% was as small as 298 to 338 nm, and the light transmittance in the short wavelength region was excellent. On the other hand, the glass material of Comparative Example 1 had a Verde constant of ⁇ 0.48 at a wavelength of 400 nm and a small absolute value. The glass material of Comparative Example 2 had a Verde constant of ⁇ 0.62 at a wavelength of 400 nm and a small absolute value. Further, the shortest wavelength at which the light transmittance reached 60% was as large as 358 nm, which was inferior to the light transmittance in the short wavelength region.
  • the glass material of the present invention is suitable as a material for a magneto-optical element constituting a magnetic device such as an optical isolator, an optical circulator, and a magnetic sensor, a magnetic glass lens used for a digital camera, a glass sheet used for a band-pass filter, and the like. is there.

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Abstract

Provided is a glass material that is capable of exhibiting both a high Faraday effect and high light transmittance in a short wavelength range. This glass material is characterized by comprising, in mol%, 30 to 50% of Pr2O3 and 0.1 to 70% of B2O3+P2O5.

Description

ガラス材及びその製造方法Glass material and manufacturing method thereof
　本発明は、光アイソレータ、光サーキュレータ、磁気センサ等の磁気デバイスを構成する磁気光学素子、デジタルカメラ等に用いられる磁性ガラスレンズ、バンドパスフィルターに用いられるガラスシートの材料等に好適なガラス材及びその製造方法に関する。 The present invention relates to a glass material suitable for a material of a magneto-optical element constituting a magnetic device such as an optical isolator, an optical circulator, a magnetic sensor, a magnetic glass lens used for a digital camera, a glass sheet used for a band-pass filter, and the like. It relates to the manufacturing method.
　常磁性化合物である酸化テルビウムを含むガラス材は、磁気光学効果の一つであるファラデー効果を示すことが知られている。ファラデー効果とは、磁場中におかれた材料を通過する直線偏光の偏光面を回転させる効果である。このような効果は光アイソレータや磁界センサなどに利用されている。 It is known that a glass material containing terbium oxide, which is a paramagnetic compound, exhibits a Faraday effect which is one of magneto-optical effects. The Faraday effect is an effect of rotating the polarization plane of linearly polarized light passing through a material placed in a magnetic field. Such effects are used in optical isolators, magnetic field sensors, and the like.
　ファラデー効果による旋光度（偏光面の回転角）θは、磁場の強さをＨ、偏光が通過する物質の長さをＬとして、以下の式により表される。式中において、Ｖは物質の種類に依存する定数であり、ベルデ定数と呼ばれる。ベルデ定数は反磁性体の場合は正の値、常磁性体の場合は負の値となる。ベルデ定数の絶対値が大きいほど、旋光度の絶対値も大きくなり、結果として大きなファラデー効果を示す。 The optical rotation (rotation angle of the polarization plane) θ by the Faraday effect is expressed by the following equation, where H is the strength of the magnetic field and L is the length of the substance through which the polarized light passes. In the formula, V is a constant depending on the type of substance, and is called Verde's constant. The Verde constant is a positive value for a diamagnetic material and a negative value for a paramagnetic material. The greater the absolute value of the Verde constant, the greater the absolute value of the optical rotation, resulting in a large Faraday effect.
　θ＝ＶＨＬ Θ = VHL
　従来、ファラデー効果を示すガラス材として、ＳｉＯ２－Ｂ２Ｏ３－Ａｌ２Ｏ３－Ｔｂ２Ｏ３系のガラス材（特許文献１参照）、Ｐ２Ｏ５－Ｂ２Ｏ３－Ｔｂ２Ｏ３系のガラス材（特許文献２参照）、あるいはＰ２Ｏ５－ＴｂＦ３－ＲＦ２（Ｒはアルカリ土類金属）系のガラス材（特許文献３参照）等が知られている。 Conventionally, as a glass material exhibiting the Faraday effect, SiO 2 —B 2 O 3 —Al 2 O 3 —Tb 2 O 3 glass material (see Patent Document 1), P 2 O 5 —B 2 O 3 —Tb 2 An O 3 glass material (see Patent Document 2), a P 2 O 5 —TbF 3 —RF 2 (R is an alkaline earth metal) glass material (see Patent Document 3), or the like is known.
特公昭５１－４６５２４号公報Japanese Patent Publication No. 51-46524 特公昭５２－３２８８１号公報Japanese Patent Publication No.52-32881 特公昭５５－４２９４２号公報Japanese Patent Publication No. 55-42942
　上記のガラス材は可視域～赤外域（例えば４２０～１５００ｎｍ）の範囲で高い透過率を示すものの、短波長域（例えば４２０ｎｍ以下）ではテルビウム元素自体による光吸収を示す。そのため、短波長域では光透過率が低下し、磁気光学デバイスの光取出し効率に劣るという問題がある。 The above glass material shows high transmittance in the visible range to infrared range (for example, 420 to 1500 nm), but shows light absorption by the terbium element itself in the short wavelength range (for example, 420 nm or less). Therefore, there is a problem that the light transmittance is reduced in a short wavelength region and the light extraction efficiency of the magneto-optical device is inferior.
　以上に鑑み、本発明は、高いファラデー効果と、短波長域における高い光透過率を両立させることが可能なガラス材を提供することを目的とする。 In view of the above, an object of the present invention is to provide a glass material capable of achieving both a high Faraday effect and a high light transmittance in a short wavelength region.
　本発明者が鋭意検討を行った結果、特定の組成を有するガラス材により前記課題を解決できることを見出した。 As a result of intensive studies by the inventors, it has been found that the above-mentioned problems can be solved by a glass material having a specific composition.
　即ち、本発明のガラス材は、モル％で、Ｐｒ２Ｏ３　３０～５０％、Ｂ２Ｏ３＋Ｐ２Ｏ５　０．１～７０％を含有することを特徴とする。ここで、「Ｂ２Ｏ３＋Ｐ２Ｏ５」は、Ｂ２Ｏ３及びＰ２Ｏ５の含有量の合量を意味する。 That is, the glass material of the present invention is characterized by containing Pr 2 O 3 30 to 50% and B 2 O 3 + P 2 O 5 0.1 to 70% in mol%. Here, “B 2 O 3 + P 2 O 5 ” means the total content of B 2 O 3 and P 2 O 5 .
　本発明のガラス材は、Ｐｒ２Ｏ３を上記の通り多量に含有することにより、ベルデ定数の絶対値が大きくなり、大きいファラデー効果を示す。また、Ｐｒ２Ｏ３は基本的に４２０ｎｍ以下（例えば２５０～４２０ｎｍ）の波長域に光吸収を示さないため、当該波長域において高い透過率を示す。 When the glass material of the present invention contains a large amount of Pr 2 O 3 as described above, the absolute value of the Verde constant increases, and a large Faraday effect is exhibited. In addition, Pr 2 O 3 basically exhibits no light absorption in a wavelength region of 420 nm or less (for example, 250 to 420 nm), and thus exhibits high transmittance in the wavelength region.
　また、ガラスの紫外吸収端が４００ｎｍ付近にあると、Ｐｒ２Ｏ３の吸収が無くとも、ガラス自体の紫外吸収が起こり、４２０ｎｍ以下での透過率の低下を招く。Ｂ２Ｏ３及びＰ２Ｏ５の少なくとも一種を必須成分として含むことで、ガラスの紫外吸収端が短波長側にシフトすることを見出したため、本発明を提案するに至った。さらに、Ｂ２Ｏ３及びＰ２Ｏ５はガラス骨格成分であるため、Ｐｒ２Ｏ３を多量に含んでもガラス化しやすいという特徴を有する。それにより、ガラス材が大径化しても結晶化しにくくなるため、生産性を向上させることが可能となる。 Further, if the ultraviolet absorption edge of the glass is in the vicinity of 400 nm, the glass itself absorbs ultraviolet light even if there is no Pr 2 O 3 absorption, leading to a decrease in transmittance at 420 nm or less. Since it has been found that the ultraviolet absorption edge of the glass shifts to the short wavelength side by including at least one of B 2 O 3 and P 2 O 5 as an essential component, the present invention has been proposed. Furthermore, since B 2 O 3 and P 2 O 5 are glass skeleton components, they have a feature that they are easily vitrified even if they contain a large amount of Pr 2 O 3 . Thereby, even if the diameter of the glass material is increased, it becomes difficult to crystallize, so that productivity can be improved.
　本発明のガラス材は、さらに、モル％で、Ａｌ２Ｏ３　０～５０％を含有することが好ましい。このようにすれば、ガラス化がより容易になる。 The glass material of the present invention preferably further contains Al 2 O 3 0 to 50% in mol%. In this way, vitrification becomes easier.
　本発明のガラス材は、厚さ１ｍｍにて、光透過率が６０％になる最短波長が３５０ｎｍ以下であることが好ましい。このようにすれば、短波長域での磁気光学デバイスの光取出し効率を向上させることができる。 The glass material of the present invention preferably has a thickness of 1 mm and a shortest wavelength at which the light transmittance is 60% is 350 nm or less. In this way, it is possible to improve the light extraction efficiency of the magneto-optical device in the short wavelength region.
　本発明のガラス材は、磁気光学素子として用いることができる。例えば、本発明のガラス材は、磁気光学素子の一種であるファラデー回転素子として用いることができる。上記の用途に用いることにより、本発明の効果を享受することができる。 The glass material of the present invention can be used as a magneto-optical element. For example, the glass material of the present invention can be used as a Faraday rotation element which is a kind of magneto-optical element. By using it for the above application, the effects of the present invention can be enjoyed.
　本発明のガラス材の製造方法は、上記のガラス材を製造するための方法であって、ガラス原料塊を空中に浮遊させて保持した状態で、ガラス原料塊を加熱融解させて溶融ガラスを得た後に、溶融ガラスを冷却する工程を備えることを特徴とする。 The method for producing a glass material of the present invention is a method for producing the above glass material, and in a state where the glass raw material lump is suspended and held in the air, the glass raw material lump is heated and melted to obtain a molten glass. And a step of cooling the molten glass.
　一般に、ガラス材は原料を坩堝等の溶融容器内で溶融し、冷却することにより作製される（溶融法）。しかしながら、本発明のガラス材は、基本的にガラス骨格を構成しないＰｒ２Ｏ３を上記の通り多量に含有する組成を有しており、ガラス化しにくい材料であるため、通常の溶融法では、溶融容器との接触界面を起点として結晶化が進行してしまう可能性がある。 Generally, a glass material is produced by melting a raw material in a melting container such as a crucible and cooling (melting method). However, the glass material of the present invention has a composition containing a large amount of Pr 2 O 3 that basically does not constitute a glass skeleton as described above, and is a material that is difficult to vitrify. Therefore, in a normal melting method, There is a possibility that crystallization proceeds from the contact interface with the melting vessel.
　ガラス化しにくい組成であっても、溶融容器との界面での接触をなくすことによりガラス化が可能となる。このような方法として、原料を浮遊させた状態で溶融、冷却する無容器浮遊法が知られている。当該方法を用いると、溶融ガラスが溶融容器にほとんど接触することがないため、溶融容器との界面を起点とする結晶化を防止することができ、ガラス化が可能となる。 Even if the composition is difficult to vitrify, it can be vitrified by eliminating contact at the interface with the melting vessel. As such a method, a containerless floating method in which a raw material is melted and cooled in a suspended state is known. When this method is used, since the molten glass hardly comes into contact with the melting vessel, crystallization starting from the interface with the melting vessel can be prevented, and vitrification becomes possible.
　本発明のガラス材は、高いファラデー効果と、短波長域における高い光透過率を両立させることが可能であり、特に短波長域での磁気光学デバイスのファラデー回転素子として好適である。 The glass material of the present invention can achieve both a high Faraday effect and a high light transmittance in a short wavelength region, and is particularly suitable as a Faraday rotating element of a magneto-optical device in a short wavelength region.
本発明のガラス材を製造するための装置の一実施形態を示す模式的断面図である。It is typical sectional drawing which shows one Embodiment of the apparatus for manufacturing the glass material of this invention.
　本発明のガラス材は、モル％で、Ｐｒ２Ｏ３　３０～５０％、Ｂ２Ｏ３＋Ｐ２Ｏ５　０．１～７０％を含有する。ガラス組成範囲をこのように限定した理由を以下に説明する。なお、以下の各成分の含有量に関する説明において、特に断りのない限り「％」は「モル％」を意味する。 The glass material of the present invention contains Pr 2 O 3 30 to 50% and B 2 O 3 + P 2 O 5 0.1 to 70% in mol%. The reason for limiting the glass composition range in this way will be described below. In the following description of the content of each component, “%” means “mol%” unless otherwise specified.
　Ｐｒ２Ｏ３はベルデ定数の絶対値を大きくしてファラデー効果を高める成分である。Ｐｒ２Ｏ３の含有量は３０～５０％であり、３０～４９％、３１～４８％、特に３２～４７％であることが好ましい。Ｐｒ２Ｏ３の含有量が少なすぎると、ベルデ定数の絶対値が小さくなり、十分なファラデー効果が得られにくくなる。一方、Ｐｒ２Ｏ３の含有量が多すぎると、ガラスの紫外吸収端が長波長側にシフトしやすい。また、ガラス化も困難となる傾向がある。 Pr 2 O 3 is a component that increases the Faraday effect by increasing the absolute value of the Verde constant. The content of Pr 2 O 3 is 30 to 50%, preferably 30 to 49%, 31 to 48%, particularly preferably 32 to 47%. When the content of Pr 2 O 3 is too small, the absolute value of the Verdet constant is reduced, a sufficient Faraday effect is difficult to obtain. On the other hand, if the content of Pr 2 O 3 is too large, the ultraviolet absorption edge of the glass tends to shift to the long wavelength side. Also, vitrification tends to be difficult.
　なお、本発明におけるＰｒ２Ｏ３の含有量は、ガラス中に存在するＰｒを全て３価の酸化物に換算して表したものである。 The content of Pr 2 O 3 in the present invention is a representation in terms of Pr present in the glass to the oxide of any trivalent.
　ベルデ定数の起源となる磁気モーメントはＰｒ４＋よりもＰｒ３＋の方が大きい。よって、ガラス材におけるＰｒ３＋の割合が大きいほど、ファラデー効果が大きくなるため好ましい。具体的には、全Ｐｒ中のＰｒ３＋の割合は、モル％で５０％以上、６０％以上、７０％以上、８０％以上、特に９０％以上であることが好ましい。 The magnetic moment that is the origin of the Verde constant is larger in Pr 3+ than in Pr 4+ . Therefore, the larger the ratio of Pr 3+ in the glass material, the greater the Faraday effect, which is preferable. Specifically, the ratio of Pr 3+ in the total Pr is preferably 50% or more, 60% or more, 70% or more, 80% or more, particularly 90% or more in mol%.
　Ｂ２Ｏ３及びＰ２Ｏ５はガラス骨格となり、ガラス化範囲を広げるための成分である。また、これらの成分を含有させることにより、紫外吸収端を短波長側にシフトすることができる。ただし、これらの成分はベルデ定数の向上には寄与しないため、含有量が多くなりすぎると十分なファラデー効果が得られにくくなる。従って、Ｂ２Ｏ３及びＰ２Ｏ５の含有量は、合量で０．１～７０％であり、０．５～６９％、１～６８％、２～６７％、３～６６％、特に４～６５％であることが好ましい。 B 2 O 3 and P 2 O 5 are components for forming a glass skeleton and expanding the vitrification range. Further, by containing these components, the ultraviolet absorption edge can be shifted to the short wavelength side. However, since these components do not contribute to the improvement of the Verde constant, if the content is too large, it is difficult to obtain a sufficient Faraday effect. Therefore, the total content of B 2 O 3 and P 2 O 5 is 0.1 to 70%, 0.5 to 69%, 1 to 68%, 2 to 67%, 3 to 66%, It is particularly preferably 4 to 65%.
　なお、Ｂ２Ｏ３及びＰ２Ｏ５の各成分の好ましい含有量は以下の通りである。 A preferable content of each component of B 2 O 3 and P 2 O 5 is as follows.
　Ｂ２Ｏ３の含有量は０～７０％（ただし７０％は含まない）、０．１～６９％、１～６８％、２～６７％、３～６６％、特に４～６５％であることが好ましい。 The content of B 2 O 3 is 0 to 70% (excluding 70%), 0.1 to 69%, 1 to 68%, 2 to 67%, 3 to 66%, particularly 4 to 65%. It is preferable.
　Ｐ２Ｏ５の含有量は０～７０％、０．１～６０％、１～５５％、２～５０％、３～４８％、４～４７％、特に５～４６％であることが好ましい。 The content of P 2 O 5 is preferably 0 to 70%, 0.1 to 60%, 1 to 55%, 2 to 50%, 3 to 48%, 4 to 47%, particularly preferably 5 to 46%. .
　本発明のガラス材には、上記成分以外にも、以下に示す種々の成分を含有させることができる。 In addition to the above components, the glass material of the present invention can contain various components shown below.
　Ａｌ２Ｏ３は中間酸化物としてガラス骨格を形成し、ガラス化範囲を広げる成分である。ただし、Ａｌ２Ｏ３はベルデ定数の向上に寄与しないため、その含有量が多すぎると十分なファラデー効果が得られにくくなる。従って、Ａｌ２Ｏ３の含有量は０～５０％、０．１～４０％、１～３０％、１～２０％、特に１～１０％であることが好ましい。 Al 2 O 3 is a component that forms a glass skeleton as an intermediate oxide and widens the vitrification range. However, since Al 2 O 3 does not contribute to the improvement of the Verde constant, if the content is too large, it becomes difficult to obtain a sufficient Faraday effect. Therefore, the content of Al 2 O 3 is preferably 0 to 50%, 0.1 to 40%, 1 to 30%, 1 to 20%, particularly 1 to 10%.
　ＳｉＯ２はガラス形成に寄与し、ガラス化範囲を広げる成分である。ただし、ＳｉＯ２が多くなると、ガラスの紫外吸収端が長波長側にシフトしやすい。そのため、ＳｉＯ２の含有量は０～４０％、０～３５％、０～３０％、０．１～２５％、特に１～２０％であることが好ましい。 SiO 2 is a component that contributes to glass formation and widens the vitrification range. However, when the amount of SiO 2 increases, the ultraviolet absorption edge of the glass tends to shift to the long wavelength side. Therefore, the content of SiO 2 is preferably 0 to 40%, 0 to 35%, 0 to 30%, 0.1 to 25%, particularly 1 to 20%.
　Ｌａ２Ｏ３、Ｇｄ２Ｏ３、Ｙｂ２Ｏ３、Ｙ２Ｏ３はガラス化の安定性を向上させる効果があるが、その含有量が多すぎるとかえってガラス化しにくくなる。また、光透過率低下の原因となる。よって、Ｌａ２Ｏ３、Ｇｄ２Ｏ３、Ｙｂ２Ｏ３、Ｙ２Ｏ３の含有量は各々１０％以下、特に５％以下であることが好ましい。 La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 , and Y 2 O 3 have the effect of improving the stability of vitrification. However, if the content is too large, it becomes difficult to vitrify. Further, it causes a decrease in light transmittance. Therefore, the contents of La 2 O 3 , Gd 2 O 3 , Yb 2 O 3 and Y 2 O 3 are each preferably 10% or less, particularly preferably 5% or less.
　Ｔｂ２Ｏ３、Ｄｙ２Ｏ３、Ｅｕ２Ｏ３、Ｃｅ２Ｏ３はベルデ定数の向上に寄与するが、光透過率低下の原因となる。よって、Ｔｂ２Ｏ３、Ｄｙ２Ｏ３、Ｅｕ２Ｏ３、Ｃｅ２Ｏ３の含有量は各々、１０％以下、５％以下、特に１％以下であることが好ましい。なお、Ｔｂ２Ｏ３、Ｄｙ２Ｏ３、Ｅｕ２Ｏ３、Ｃｅ２Ｏ３の含有量は、ガラス中に存在するＴｂ、Ｄｙ、Ｅｕ、Ｃｅを全て３価の酸化物に換算して表したものである。 Tb 2 O 3 , Dy 2 O 3 , Eu 2 O 3 , and Ce 2 O 3 contribute to the improvement of the Verde constant, but cause a decrease in light transmittance. Therefore, the contents of Tb 2 O 3 , Dy 2 O 3 , Eu 2 O 3 , and Ce 2 O 3 are each preferably 10% or less, 5% or less, and particularly preferably 1% or less. The contents of Tb 2 O 3 , Dy 2 O 3 , Eu 2 O 3 , and Ce 2 O 3 are expressed by converting Tb, Dy, Eu, and Ce present in the glass into trivalent oxides. It is a thing.
　ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯはガラス化の安定性と化学的耐久性を高める効果がある。ただし、ベルデ定数の向上に寄与しないため、その含有量が多すぎると十分なファラデー効果が得られにくくなる。従って、これらの成分の含有量は各々０～１０％、特に０～５％であることが好ましい。 MgO, CaO, SrO, and BaO have the effect of improving the stability and chemical durability of vitrification. However, since it does not contribute to the improvement of the Verde constant, if the content is too large, it becomes difficult to obtain a sufficient Faraday effect. Accordingly, the content of these components is preferably 0 to 10%, particularly 0 to 5%.
　Ｇａ２Ｏ３はガラス形成能を高め、ガラス化範囲を広げる効果を有する。ただし、その含有量が多すぎると失透しやすくなる。また、Ｇａ２Ｏ３はベルデ定数の向上に寄与しないため、その含有量が多すぎると十分なファラデー効果が得られにくくなる。従って、Ｇａ２Ｏ３の含有量は０～６％、特に０～５％であることが好ましい。 Ga 2 O 3 has the effect of increasing the glass forming ability and expanding the vitrification range. However, when there is too much the content, it will become easy to devitrify. Further, since the Ga 2 O 3 it does not contribute to the improvement of the Verdet constant, when the content is too large, a sufficient Faraday effect difficult to obtain. Therefore, the Ga 2 O 3 content is preferably 0 to 6%, particularly preferably 0 to 5%.
　フッ素はガラス形成能を高め、ガラス化範囲を広げる効果を有する。ただし、その含有量が多すぎると溶融中に揮発して組成変動を引き起こしたり、ガラス化の安定性に悪影響を及ぼす恐れがある。従って、フッ素の含有量（Ｆ２換算）は０～１０％、０～７％、特に０～５％であることが好ましい。 Fluorine has the effect of increasing the glass forming ability and expanding the vitrification range. However, if its content is too large, it may volatilize during melting and cause composition fluctuations, or it may adversely affect the stability of vitrification. Accordingly, the fluorine content (F 2 conversion) is preferably 0 to 10%, 0 to 7%, particularly preferably 0 to 5%.
　還元剤としてＳｂ２Ｏ３を添加することができる。ただし、着色を避けるため、あるいは環境への負荷を考慮して、Ｓｂ２Ｏ３の含有量は０．１％以下であることが好ましい。 Sb 2 O 3 can be added as a reducing agent. However, the content of Sb 2 O 3 is preferably 0.1% or less in order to avoid coloring or in consideration of environmental load.
　本発明のガラス材は、特に光アイソレータ、光サーキュレータ、磁気センサ等の磁気光学素子として使用する場合に、紫外吸収端が短波長であることが好ましい。そのため、厚さ１ｍｍにて、光透過率が６０％になる最短波長が３５０ｎｍ以下、３４５ｎｍ以下、３４０ｎｍ以下、３３０ｎｍ以下、３２０ｎｍ以下、特に３００ｎｍ以下であることが好ましい。なお、この光透過率は反射も含んだ外部透過率である。 When the glass material of the present invention is used as a magneto-optical element such as an optical isolator, an optical circulator, or a magnetic sensor, it is preferable that the ultraviolet absorption edge has a short wavelength. Therefore, it is preferable that the shortest wavelength at which the light transmittance is 60% at a thickness of 1 mm is 350 nm or less, 345 nm or less, 340 nm or less, 330 nm or less, 320 nm or less, particularly 300 nm or less. This light transmittance is an external transmittance including reflection.
　本発明のガラス材は、例えば無容器浮遊法により作製することができる。図１は、無容器浮遊法によりガラス材を作製するための製造装置の一例を示す模式的断面図である。以下、図１を参照しながら、本発明のガラス材の製造方法について説明する。 The glass material of the present invention can be produced by, for example, a containerless floating method. FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing apparatus for producing a glass material by a containerless floating method. Hereinafter, the manufacturing method of the glass material of this invention is demonstrated, referring FIG.
　ガラス材の製造装置１は成形型１０を有する。成形型１０は溶融容器としての役割も果たす。成形型１０は、成形面１０ａと、成形面１０ａに開口している複数のガス噴出孔１０ｂとを有する。ガス噴出孔１０ｂは、ガスボンベなどのガス供給機構１１に接続されている。このガス供給機構１１からガス噴出孔１０ｂを経由して、成形面１０ａにガスが供給される。ガスの種類は特に限定されず、例えば、空気や酸素であってもよいし、窒素ガス、アルゴンガス、ヘリウムガス、一酸化炭素ガス、二酸化炭素ガス、水素を含有した還元性ガスであってもよい。 The glass material manufacturing apparatus 1 has a mold 10. The mold 10 also serves as a melting container. The molding die 10 has a molding surface 10a and a plurality of gas ejection holes 10b opened in the molding surface 10a. The gas ejection hole 10b is connected to a gas supply mechanism 11 such as a gas cylinder. Gas is supplied from the gas supply mechanism 11 to the molding surface 10a via the gas ejection hole 10b. The type of gas is not particularly limited, and may be, for example, air or oxygen, or a reducing gas containing nitrogen gas, argon gas, helium gas, carbon monoxide gas, carbon dioxide gas, or hydrogen. Good.
　製造装置１を用いてガラス材を製造するに際しては、まず、ガラス原料塊１２を成形面１０ａ上に配置する。ガラス原料塊１２としては、例えば、原料粉末をプレス成型等により一体化したものや、原料粉末をプレス成型等により一体化した後に焼結させた焼結体や、目標ガラス組成と同等の組成を有する結晶の集合体等が挙げられる。 When manufacturing a glass material using the manufacturing apparatus 1, the glass raw material lump 12 is first arrange | positioned on the molding surface 10a. As the glass raw material block 12, for example, a raw material powder integrated by press molding or the like, a sintered body obtained by integrating raw material powder by press molding or the like, and a composition equivalent to the target glass composition are used. For example, an aggregate of crystals.
　次に、ガス噴出孔１０ｂからガスを噴出させることにより、ガラス原料塊１２を成形面１０ａ上で浮遊させる。すなわち、ガラス原料塊１２を、成形面１０ａに接触していない状態で保持する。その状態で、レーザー光照射装置１３からレーザー光をガラス原料塊１２に照射する。これによりガラス原料塊１２を加熱溶融してガラス化させ、溶融ガラスを得る。その後、溶融ガラスを冷却することにより、ガラス材を得ることができる。ガラス原料塊１２を加熱溶融する工程と、溶融ガラス、さらにはガラス材の温度が少なくとも軟化点以下となるまで冷却する工程においては、少なくともガスの噴出を継続し、ガラス原料塊１２、溶融ガラス、さらにはガラス材と成形面１０ａとの接触を抑制することが好ましい。なお、磁場を印加することにより発生する磁力を利用してガラス原料塊１２を成形面１０ａ上に浮遊させてもよい。また、加熱溶融する方法としては、レーザー光を照射する方法以外にも、輻射加熱であってもよい。 Next, the glass raw material block 12 is floated on the molding surface 10a by ejecting gas from the gas ejection holes 10b. That is, the glass raw material block 12 is held in a state where it is not in contact with the molding surface 10a. In this state, the glass material block 12 is irradiated with laser light from the laser light irradiation device 13. Thereby, the glass raw material lump 12 is heated and melted to be vitrified to obtain molten glass. Thereafter, the glass material can be obtained by cooling the molten glass. In the step of heating and melting the glass raw material lump 12 and the step of cooling until the temperature of the molten glass and further the glass material is at least the softening point or less, at least gas ejection is continued, and the glass raw material lump 12, molten glass, Furthermore, it is preferable to suppress contact between the glass material and the molding surface 10a. In addition, you may float the glass raw material lump 12 on the molding surface 10a using the magnetic force which generate | occur | produces by applying a magnetic field. In addition to the method of irradiating laser light, the method of heating and melting may be radiant heating.
　なお、本発明のガラス材は磁化率が高いため、本発明のガラス材をモールドプレス成型等によりレンズ形状に成型することによって、デジタルカメラやカメラ付携帯電話等のオートフォーカス用レンズ等に用いることができる。これらのカメラには、カメラの焦点距離を変える、つまり、オートフォーカス用レンズを所定の位置に移動させるための駆動装置が設けられており、従来、駆動装置には、レンズを固定するためのレンズホルダー、レンズホルダーを移動させるためのばねが備えられている。しかしながら、レンズホルダーやばねを備えた駆動装置では、デジタルカメラやカメラ付携帯電話型等を小型化することができない。しかしながら、磁化率の高い本発明のガラス材でレンズを作製すれば、磁石によってレンズ自体を移動させることができるため、レンズホルダーやばねが不要となりカメラ等を小型化することが可能になる。 In addition, since the glass material of the present invention has a high magnetic susceptibility, the glass material of the present invention is used for autofocus lenses such as digital cameras and camera-equipped mobile phones by molding into a lens shape by mold press molding or the like. Can do. These cameras are provided with a driving device for changing the focal length of the camera, that is, for moving the autofocus lens to a predetermined position. Conventionally, the driving device has a lens for fixing the lens. A spring for moving the holder and the lens holder is provided. However, in a driving device including a lens holder and a spring, a digital camera, a camera-equipped mobile phone type, or the like cannot be downsized. However, if a lens is made of the glass material of the present invention having a high magnetic susceptibility, the lens itself can be moved by a magnet, so that a lens holder and a spring are not required, and the camera and the like can be miniaturized.
　また、本発明のガラス材は、２５０～４２０ｎｍの波長域の光透過率が４２０～５００ｎｍの波長域の光透過率より高く、５００～５５０ｎｍの波長域の光透過率が５５０～６２０ｎｍの光透過率より高く、６２０～９５０ｎｍの波長域の光透過率が９５０～１２００ｎｍの波長域の光透過率よりも高い。このように、特定の波長域の光を吸収する性質を有するため、本発明のガラス材を研磨等によりシート形状にすることにより、バンドパスフィルターとして使用することが可能である。 Further, the glass material of the present invention has a light transmittance in the wavelength region of 250 to 420 nm higher than that in the wavelength region of 420 to 500 nm, and a light transmittance of 550 to 620 nm in the wavelength region of 500 to 550 nm. The light transmittance in the wavelength range of 620 to 950 nm is higher than the light transmittance in the wavelength range of 950 to 1200 nm. Thus, since it has the property of absorbing light in a specific wavelength region, it can be used as a band-pass filter by forming the glass material of the present invention into a sheet shape by polishing or the like.
　以下、本発明を実施例に基づいて説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.
　表１は本発明の実施例及び比較例を示している。 Table 1 shows examples and comparative examples of the present invention.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　各試料は次のようにして作製した。まず表に示すガラス組成になるように調合した原料をプレス成型し、８００～１４００℃で６時間焼結することによりガラス原料塊を作製した。 Each sample was prepared as follows. First, raw materials prepared so as to have the glass composition shown in the table were press-molded, and sintered at 800 to 1400 ° C. for 6 hours to prepare glass raw material blocks.
　次に、乳鉢中でガラス原料塊を粗粉砕し、０．０５～１．５ｇの小片とした。得られたガラス原料塊の小片を用いて、図１に準じた装置を用いた無容器浮遊法によってガラス材（直径約１～１０ｍｍ）を作製した。なお、熱源としては１００ＷのＣＯ２レーザー発振器を用いた。また、原料塊を空中に浮遊させるためのガスとして窒素ガスを用い、流量１～３０Ｌ／分で供給した。 Next, the glass raw material lump was coarsely pulverized in a mortar to obtain small pieces of 0.05 to 1.5 g. Using the obtained piece of glass raw material lump, a glass material (diameter: about 1 to 10 mm) was produced by a containerless floating method using an apparatus according to FIG. A 100 W CO 2 laser oscillator was used as the heat source. Further, nitrogen gas was used as a gas for suspending the raw material lump in the air and was supplied at a flow rate of 1 to 30 L / min.
　得られたガラス材について、カー（Ｋｅｒｒ）効果測定装置（日本分光（株）製、品番：Ｋ－２５０）を用いてベルデ定数を測定した。具体的には、得られたガラス材を１ｍｍ程度の厚さとなるよう研磨加工し、１５ｋＯｅの磁場中で波長４００～８５０ｎｍでのファラデー回転角を測定し、波長４００ｎｍにおけるベルデ定数を算出した。なお、波長の掃引速度は６ｎｍ／分とした。結果を表１に示す。 The Verde constant of the obtained glass material was measured using a Kerr effect measuring device (manufactured by JASCO Corporation, product number: K-250). Specifically, the obtained glass material was polished to a thickness of about 1 mm, the Faraday rotation angle at a wavelength of 400 to 850 nm was measured in a magnetic field of 15 kOe, and the Verde constant at a wavelength of 400 nm was calculated. The wavelength sweep rate was 6 nm / min. The results are shown in Table 1.
　光透過率が６０％になる最短波長は、得られたガラス材を１ｍｍの厚さとなるよう研磨加工し、分光光度計（島津製作所製ＵＶ－３１００）を用いて測定した。なお、光透過率は反射も含んだ外部透過率である。 The shortest wavelength at which the light transmittance was 60% was measured using a spectrophotometer (Shimadzu UV-3100) after polishing the obtained glass material to a thickness of 1 mm. The light transmittance is an external transmittance including reflection.
　表１から明らかなように実施例１～５のガラス材は、波長４００ｎｍにおけるベルデ定数が－０．７４～－１．８７であり、絶対値が大きかった。また、光透過率が６０％になる最短波長は２９８～３３８ｎｍと小さく、短波長域における光透過率に優れていた。一方、比較例１のガラス材は、波長４００ｎｍにおけるベルデ定数が－０．４８であり、絶対値が小さかった。比較例２のガラス材は、波長４００ｎｍにおけるベルデ定数が－０．６２であり、絶対値が小さかった。また、光透過率が６０％になる最短波長は３５８ｎｍと大きく、短波長域における光透過率に劣っていた。 As is clear from Table 1, the glass materials of Examples 1 to 5 had a Verde constant of −0.74 to −1.87 at a wavelength of 400 nm, and had a large absolute value. Further, the shortest wavelength at which the light transmittance reached 60% was as small as 298 to 338 nm, and the light transmittance in the short wavelength region was excellent. On the other hand, the glass material of Comparative Example 1 had a Verde constant of −0.48 at a wavelength of 400 nm and a small absolute value. The glass material of Comparative Example 2 had a Verde constant of −0.62 at a wavelength of 400 nm and a small absolute value. Further, the shortest wavelength at which the light transmittance reached 60% was as large as 358 nm, which was inferior to the light transmittance in the short wavelength region.
　本発明のガラス材は、光アイソレータ、光サーキュレータ、磁気センサ等の磁気デバイスを構成する磁気光学素子、デジタルカメラ等に用いられる磁性ガラスレンズ、バンドパスフィルターに用いられるガラスシートの材料等として好適である。 The glass material of the present invention is suitable as a material for a magneto-optical element constituting a magnetic device such as an optical isolator, an optical circulator, and a magnetic sensor, a magnetic glass lens used for a digital camera, a glass sheet used for a band-pass filter, and the like. is there.
　　１：ガラス材の製造装置
　　１０：成形型
　　１０ａ：成形面
　　１０ｂ：ガス噴出孔
　　１１：ガス供給機構
　　１２：ガラス原料塊
　　１３：レーザー光照射装置 1: Glass material manufacturing apparatus 10: Mold 10a: Molding surface 10b: Gas ejection hole 11: Gas supply mechanism 12: Glass raw material block 13: Laser beam irradiation apparatus

Claims (6)

  1. 　モル％で、Ｐｒ２Ｏ３　３０～５０％、Ｂ２Ｏ３＋Ｐ２Ｏ５　０．１～７０％を含有することを特徴とするガラス材。 A glass material comprising Pr 2 O 3 30 to 50% and B 2 O 3 + P 2 O 5 0.1 to 70% by mol%.
  2. 　さらに、モル％で、Ａｌ２Ｏ３　０～５０％を含有することを特徴とする請求項１に記載のガラス材。 The glass material according to claim 1, further comprising 0 to 50% of Al 2 O 3 in mol%.
  3. 　厚さ１ｍｍにて、光透過率が６０％になる最短波長が３５０ｎｍ以下であることを特徴とする請求項１～２に記載のガラス材。 3. The glass material according to claim 1, wherein the shortest wavelength at which the light transmittance is 60% at a thickness of 1 mm is 350 nm or less.
  4. 　磁気光学素子として用いられることを特徴とする請求項１～３のいずれか一項に記載のガラス材。 The glass material according to any one of claims 1 to 3, wherein the glass material is used as a magneto-optical element.
  5. 　ファラデー回転素子として用いられることを特徴とする請求項４に記載のガラス材。 The glass material according to claim 4, wherein the glass material is used as a Faraday rotation element.
  6. 　請求項１～５のいずれか一項に記載のガラス材を製造するための方法であって、ガラス原料塊を空中に浮遊させて保持した状態で、前記ガラス原料塊を加熱融解させて溶融ガラスを得た後に、前記溶融ガラスを冷却する工程を備えることを特徴とする、ガラス材の製造方法。 A method for producing the glass material according to any one of claims 1 to 5, wherein the glass raw material mass is heated and melted in a state where the glass raw material mass is suspended and held in the air. The manufacturing method of the glass material characterized by including the process of cooling the said molten glass after obtaining.
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